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Updated: Sep 12, 2025

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

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Published on: January 17, 2020

Evolución dirigida de las enzimas no hémicas sustituidas por cobre para la metilación enantioselectiva de alqueno

James G Zhang¹, Xiongyi Huang¹

¹Department of Chemistry, Johns Hopkins University; Baltimore, Maryland 21218, United States.

Journal of the American Chemical Society

|August 5, 2025

Resumen

Los investigadores desarrollaron un nuevo método biocatalítico para sintetizar lactonas trifluorometiladas utilizando una enzima modificada. Este avance ofrece una nueva herramienta para crear valiosos compuestos de organofluoro de manera eficiente y con un alto control estéreo.

Área de la Ciencia:

Biocatálisis
Química del fluoro orgánico
Ingeniería de enzimas

Sus antecedentes:

La trifluorometilación es crucial para el desarrollo de nuevos productos farmacéuticos y materiales.
Las enzimas capaces de catalizar la trifluorometilación (trifluorometilasas) son raras, lo que limita los enfoques biocatalíticos.
Los métodos existentes para introducir el grupo trifluorometilo a menudo requieren condiciones adversas o reactivos tóxicos.

Objetivo del estudio:

Establecer una plataforma biocatalítica para la síntesis de lactonas trifluorometiladas.
Para diseñar una enzima capaz de la oxitrifluorometilación intramolecular de alqueno.
Ampliar el ámbito de aplicación de la biocatálisis en la síntesis del organofluoruro.

Principales métodos:

Se utilizó hidroximandelato sintasa (AoHMS) de Amycolatopsis orientalis, una enzima de hierro no hemo.
Reemplazó el centro catalítico de hierro nativo con cobre para aprovechar la actividad de oxigenación del cobre.
Evolución dirigida empleada para optimizar el AoHMS sustituido por cobre para una mayor actividad y selectividad.

Principales resultados:

Se desarrolló una variante de AoHMS sustituida por cobre para una eficiente metilación intramolecular de alqueno oxitrifluoro.
Se han producido con éxito β-, γ- y δ-lactonas con estereocentros cuaternarios.
Se obtiene un alto rendimiento (hasta el 99%) y un excelente control de enantio (hasta 98,51,5 e.r. En el caso de los

Conclusiones:

Se ha demostrado una nueva plataforma biocatalítica para la construcción de lactonas sustituidas por CF3.
Destacó el potencial de las enzimas de hierro no hemo sustituidas por metales para crear transformaciones nuevas en la naturaleza.
Se ha ampliado la caja de herramientas biocatalíticas para la síntesis de valiosos compuestos de organofluoro.

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